CN101909729B - Ozonolysis reactions in liquid CO2 and CO2-expanded solvents - Google Patents

Ozonolysis reactions in liquid CO2 and CO2-expanded solvents Download PDF

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CN101909729B
CN101909729B CN200880123965.2A CN200880123965A CN101909729B CN 101909729 B CN101909729 B CN 101909729B CN 200880123965 A CN200880123965 A CN 200880123965A CN 101909729 B CN101909729 B CN 101909729B
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ozone
liquid
acid
pressure
critical
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CN101909729A (en
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巴拉·萨布拉马尼亚姆
达里尔·布希
安德鲁·M·丹拜
托马斯·P·宾德
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Archer Daniels Midland Co
University of Kansas
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University of Kansas
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/10—Preparation of ozone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • C07D323/02—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D501/00—Heterocyclic compounds containing 5-thia-1-azabicyclo [4.2.0] octane ring systems, i.e. compounds containing a ring system of the formula:, e.g. cephalosporins; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
    • C07D501/14—Compounds having a nitrogen atom directly attached in position 7
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/14—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/106—Ozone
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

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  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
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Abstract

A method for increasing ozone concentration in a liquid can include: providing a gas having ozone; introducing the ozone-containing gas into a liquid, wherein the liquid and ozone combination has a temperature between about 0.8 and about 1.5 times the critical temperature of ozone; and increasing isothermally, the pressure of the ozone-containing gas above the liquid to about 0.3 to about 5 times the critical pressure of ozone so as to increase the ozone concentration in the liquid. The temperature is expressed in absolute units (Kelvin or Rankin). The method can be used for removing ozone from a gas or for purifying ozone. The liquid having a high ozone concentration can be used for ozonolysis of a substrate.

Description

At liquid CO 2and CO 2ozonolysis reactions in expanded solvents
Background technology
Traditional ozonolysis reactions makes O by bubbling 3by a kind of water that comprises substrate or organic liquid, to be chemically modified, for example, comprise the molecule of carbon-to-carbon double bond (being C=C).Yet this conventional process has some shortcomings.The first, due to O 3height can react, thereby the reaction temperature adopting is generally lower than room temperature (approximately 0 ℃ conventionally), wherein, and O 3solubility in this liquid phase is lower, although it is greater than the solubility of dioxygen conventionally.For example, under 0 ℃ and 1.013bar pressure, O 3solubility in water is 0.105x10 -2g/mL.Secondly, O 3with many conventional organic solvent chemically reactives, this has not only weakened O 3for being oxidized the validity of this substrate, and cause undesirable product from solvent oxidation effect (for example, refuse) to form and the increase of solvent use amount.The 3rd, O 3solubility in this liquid phase is not adjustable delicately because of pressure, and this has limited the ability of control response speed and product selectivity conventionally.
Thereby obtaining a kind of employing increases O 3solubility in solvent and the method and the reaction condition that carry out ozone decomposed will be useful.In addition, obtain a kind of with respect to O 3be essentially in the solvent of inertia and carry out ozone decomposed and do not expect that with restriction the number of byproduct and the method for amount and reaction condition will be also useful.Further, under following method and reaction condition, carrying out ozone decomposed will be also useful, wherein, and O 3solubility in this liquid phase is adjustable with pressure, to the ability of control response speed and product selectivity is provided.
Summary of the invention
In a specific embodiment, the present invention includes a kind of method for increasing ozone concentration in liquid.The method comprises: a kind of gas that contains ozone is provided; The gas that this is contained to ozone is incorporated in a kind of liquid, and wherein, this liquid and combined with ozone thing have about 0.8 temperature to about 1.5 times of ozone critical-temperatures; Isothermal increase this liquid top the gas that contains ozone pressure to about 0.3 to about 5 times of ozone critical pressures to increase the concentration of ozone in this liquid.Equally, temperature can be about 1 to about 1.2 times of ozone critical-temperatures, and wherein this temperature represents with Kelvin.In addition, pressure can be added to about 0.5 to about 2 times of ozone critical pressures, and wherein this pressure represents with bar (bars).Ozone concentration in this liquid is minimum is increased about 5 times, on half order of magnitude, or is increased to approximately one more than the order of magnitude.Certainly, the scope of temperature and pressure can convert other unit representation to.
In a specific embodiment, this liquid can comprise liquid carbon dioxide, liquid light hydrocarbon (for example, C 4or lower), methyl alcohol, ethanol, alcohols, hexane, liquid SF 6, liquid xenon, water, fluorocarbon solvent, high oxidation molecule, highly fluorinated molecule, CF 3cO 2h, ionic liquid, strong liquid acids, H 2sO 4, HSO 3f, HSO 3cF 3, organic acid, saturated hydrocarbons or its composition any one.Equally, this liquid can be a kind of carbon dioxide expanded liquid of aforesaid liquid.
In a specific embodiment, the present invention can comprise a kind of for extract the method for ozone from gas.This method can comprise: the gas that contains ozone of a kind of temperature the ozone critical-temperature of about 0.8 to about 1.5 times is provided; The pressure that increases this ozone under isothermy to about 0.3 times to about 5 times of ozone critical pressures; The ozone of this compression is introduced to a kind of liquid, and wherein, this liquid and combined with ozone thing have at about 0.8 temperature to about 1.5 times of ozone critical-temperatures and about 0.3 pressure to about 5 times of ozone critical pressures.Temperature and pressure can be described herein.Equally, liquid and carbon dioxide expanded liquid can be described herein.
In a specific embodiment, the present invention can comprise a kind of method of carrying out ozone decomposed on molecule in liquid.This method can comprise: a kind of composition that contains liquid and ozone is provided, wherein, this liquid and combined with ozone thing have at about 1 temperature to about 1.2 times of ozone critical-temperatures and about 0.5 pressure to about 2 times of ozone critical pressures, wherein, this molecule is dissolved or be dispersed in this liquid; Make this molecule and ozone reaction.The method can further comprise introduces following one by this molecule: the liquid of not introducing ozone; Do not import the ozone in liquid; Or the composition of liquid and ozone.Temperature and pressure can be described herein.Equally, liquid and carbon dioxide expanded liquid can be described herein.
In a specific embodiment, ozone decomposed can further comprise: ozone is introduced to this liquid, and wherein this liquid and combined with ozone thing have about 0.8 temperature to about 1.5 times of ozone critical-temperatures; The pressure that isothermal increases this ozone to about 0.3 to about 5 times of ozone critical pressures to increase the ozone concentration in liquid.
In a specific embodiment, the group that the molecule of this experience ozone decomposed can select freely following material to form: there is the molecule of unsaturated hydrocarbons, the molecule with carbon-to-carbon double bond, unsaturated hydrocarbons acid, methyl oleate, oil, fat, soya-bean oil, unrighted acid, vegetablefats acid, fatty acid ester, fatty acid amide, alkene, steroidal, benzyl, there is allylic molecule, terpenes, cynnematin, cephalosporins derivatives, tertiary allyl alcohol etc.
In a specific embodiment, the present invention can comprise a kind of for carry out the fluid composition of ozone decomposed on molecule, this fluid composition be a kind of liquid as the composition of liquid carbon dioxide or carbon dioxide expanded liquid and ozone, and have about 1 to the temperature of about 1.2 times of ozone critical-temperatures and about 0.5 pressure to about 2 times of ozone critical pressures.Said composition also can comprise this molecule that experiences ozone decomposed.Temperature and pressure can be described herein.Equally, liquid and carbon dioxide expanded liquid can be described herein.
In a specific embodiment, this fluid composition has following characteristic: it absorbs spectral coverage λ maxat about 253.7nm, approximately 577nm and 603nm, wherein, when pressure is during lower than about 0.5 times of ozone critical pressure, at least one λ maxthe ODU with about 0.005 unit; When pressure is when arriving about 2 times of ozone critical pressures for about 0.5 times, this λ maxthere is about 0.01 to about 0.1 ODU.
In a specific embodiment, the present invention can comprise a kind of method for the separated ozone of air or oxygen from containing ozone.This method can comprise: provide a kind of its temperature on ozone critical-temperature and the bag of pressure under ozone critical pressure gas ozoniferous; Change the temperature of this gas to the temperature that is approximately equal to or less than greatly ozone critical-temperature; The pressure that increases this gas to about ozone critical pressure with separated ozone from this gas.Temperature and pressure can be described herein.Equally, liquid and carbon dioxide expanded liquid can be described herein.Selectable, in the situation that this gas exists in a kind of liquid, ozone is separated and enter this liquid from this gas.
The feature of these and other specific embodiment and this sensor device will be showed from following explanation and accessory claim more fully, or is learned by the application of the sensor device of illustrating hereinafter.
Above-mentioned general introduction is just illustrative, does not mean the restriction of any mode.Except this illustrative aspect, the specific embodiment and feature as above, further aspect, the specific embodiment and feature are with reference to accompanying drawing and following detailed description performance.
Accompanying drawing explanation
For further illustrating above-mentioned and other advantage and the feature of the composition of this ozonolysis reactions device equipment and charging and reactant mixture, with reference to accompanying drawing, give one of this ozonolysis reactions device equipment and describe intuitively.These accompanying drawings of describing are only the specific embodiment that illustrates this ozonolysis reactions device equipment, thereby can not be considered the scope that limits it.Similarly, accompanying drawing will can not be regarded as limiting shape or size and the feature of any object of the present invention, for example when need or when definite this ozonolysis reactions device equipment can there are different shape and size.
Accompanying drawing 1A-1C is sketch map (the Kirk-Othmer Encyclopedia of Chemical Technology 4 of ozonolysis reactions thedition, John Wiley and Sons, New York 8124-125 (1996)).
Accompanying drawing 2A-2E is the sketch map of ozonolysis reactions.
Accompanying drawing 3 is for carrying out ozone decomposed or from the purify schematic diagram of a device of ozone of a kind of gas.
Accompanying drawing 4A-4B shows the ultraviolet ray/visible spectrum of this ozone, and it has strong absorption Hartley absorption band and weak absorption Chappuis absorption band.
Accompanying drawing 5 is that a spectrogram shows and added (by supercharging) to the liquid CO of a fixed volume when ozone 2time the Chappuis absorption band increase that absorbs.
Accompanying drawing 6 is one to show and added (by supercharging) to the liquid CO of fixed volume when ozone/air or ozone/oxygen mixture 2time ozone concentration to P totalgraph of a relation.
Accompanying drawing 7 is one to show and be added into liquid CO when ozone 2time the Chappuis absorption band increase that absorbs figure.
Accompanying drawing 8 is one to show and be added into liquid CO when ozone 2time ozone concentration to P totalgraph of a relation.
Accompanying drawing 9 is one to show CO 2the figure of the temperature effect expanding at methyl alcohol/soya-bean oil binary composition (molar ratio 6: 1).
Accompanying drawing 10 is one to show the figure of the ultraviolet ray/visible spectrum of CXL methyl alcohol while adding ozone.
Accompanying drawing 11 is one to show the figure of the ultraviolet ray/visible spectrum of CXL hexane while adding ozone.
Accompanying drawing 12 is one to show the figure of the ultraviolet ray/visible spectrum of the liquid methyl alcohol when 1.013bar adds ozone.
Accompanying drawing 13 is one to show the figure of the ultraviolet ray/visible spectrum of the ozonisation methyl alcohol while adding methyl oleate.
Accompanying drawing 14 is one to show the figure of the ultraviolet ray/visible spectrum of the methyl oleate in methyl alcohol while adding ozone.
Accompanying drawing 15 is that one to show in temperature be the size figure relevant with pressure of the solubility of ozone in water under the isothermy of 2 ℃.
Accompanying drawing 16 is that one to show in temperature be the size figure relevant with pressure of the solubility of ozone in water under the isothermy of 6 ℃.
Accompanying drawing 17 is that one to show in temperature be the size figure relevant with pressure of the solubility of ozone in water under the isothermy of 20 ℃.
Accompanying drawing 18 is schematic diagrames of a device that has a ultrasonic probe during ozone decomposed or when purifying ozone from a gas and stir for generation of ultrasonic wave.
Accompanying drawing 19 is one to show figure (Kang, J-W., the Lee of the speed that ozone decomposes in water when having and do not have ultrasonic wave to stir, K-H., Koh, C-I., Nam, S-N., Korean Journal of Chemical Engineering 18336 (2001)).
Accompanying drawing 20 is shown the form that a demonstration ultrasonic wave stirs impact, has wherein listed ozone in water and the speed constant of decomposing in liquid carbon dioxide.
The specific embodiment
In detailed description below, the part that Reference numeral is accompanying drawing.In the accompanying drawings, the identical same parts of the general expression of mark, unless context is stipulated in addition.The illustrative specific embodiment in this detailed description, accompanying drawing and claim is not limited to.Do not departing under the condition of theme tone of the present invention or protection domain, other the specific embodiment can be utilized, and also can carry out other change.
I. preface
Briefly say, the present invention includes for increasing ozone concentration in liquid with for implementing the new method of ozonolysis reactions.Ozone has critical-temperature (Tc)-12.15 ℃ (261K), critical pressure (Pc) 55.73bar, critical density (ρ c) 540kg/m 3.In ozone decomposed process, substrate (molecule that for example, contains C=C) is dissolved or emulsified in liquid carbon dioxide or carbon dioxide expanded solvent.In order to increase the ozone concentration in liquid, that in an ozone generator, utilizes that air or oxygen produces comprises ozone (O 3) air-flow, at 1-1.2 times of O preferably approximately 3at the temperature of critical-temperature (representing with K), be added into this liquid phase (for example, liquid carbon or carbon dioxide expanded solvent).Preferably, ozone is compressed to about 0.5-2 times O 3the pressure of critical pressure.When pressure is increased to 65bar from about 51bar, O 3solubility increase in liquid carbon dioxide approaches an order of magnitude.Under these conditions, show, when mixing with liquid carbon dioxide, O 3stable, and O 3can in substrate, disconnect carbon-to-carbon double bond, the base-material in those bio-refineries especially, produce for the synthesis of the construction unit of various industrial chemicals.This Reaction pathway intermediate carries out, and this intermediate is metastable, but the further oxidation after this main ozone oxidation or the low-qualityer molecule of generation that reduces, it is applicable to conventionally as the construction unit for chemical synthesis.For instance, show methyl oleate, CH 3(CH 2) 7cH=CH (CH 2) 7c (=O) OCH 3ozone decomposed in liquid carbon dioxide and carbon dioxide expanded liquid produces carboxylic acid, dicarboxylic acids and aldehyde.
Ozone decomposed method of the present invention is used in substrate and breaks carbon-to-carbon double bond, the base-material in those bio-refineries especially, produce for the synthesis of the construction unit of various industrial chemicals.This Reaction pathway intermediate carries out, and this intermediate is metastable, but the further oxidation after this main ozone oxidation or the low-qualityer molecule of generation that reduces, it is applicable to conventionally as the construction unit for chemical synthesis.In liquid carbon dioxide, density of ozone increases the critical point close to it significantly, this allow for special object, to increase the solubility of ozone and in liquid phase, adjust ozone concentration ability.Meanwhile, at the bottom of ozone is preferably oxidized a lot of alkylenes in carbon dioxide and CXL.For the ozonisation of methyl oleate, this solvent system produces following material: in carbon dioxide, produce aldehyde C-9, n-nonanoic acid and azelaic acid; In carbon dioxide expanded n-hexane, produce nonyl alcohol, n-nonanoic acid, azelaic acid; With in carbon dioxide expanded methyl alcohol, produce azelaic acid and n-nonanoic acid.
The significant feature of this new method is as follows: (i) O 3in this preferred solvent, be stable; Due to its non-reacted under preferred reaction conditions, (ii) under this preferable reaction temperature, O 3solubility in this solvent can increase an order of magnitude and pressure change is minimum, and this adjustability provides the ability of control response speed and product selectivity; (iii) combustibility reducing is dangerous; (iv) solvent low toxicity; (v) product is easily separated.
Due to its high oxidation electromotive force (in acid, E o=2.075V; In alkali, E o=1.246V), ozone has been used as optimum oxidant research on powerful and an environment, because it is finally decomposed into aerial oxygen.For example, methyl oleate, CH 3(CH 2) 7cH=CH (CH 2) 7c (=O) OCH 3ozone decomposed, the output that has obtained aldehyde succeeded by the catalytic reduction in water approaches 90%.Studying in great detail of this metastable initial oxidation product show, 90% methyl oleate is converted into 1,2,4-, tri-butyl oxide links (trioxolane), in addition 10% produce peroxide oligomer (accompanying drawing 1A).The latter should be attended by the aldehyde of same equimolar amounts.This 1,2,4-tri-butyl oxide links (trioxolane) are the initial product to 1,3 addition of this pair of key by ozone, 1,2,3-, tri-butyl oxide links (trioxolane) reset to form.Those rearrangements can be understood as and by a reversible decomposition method, form that an aldehyde and zwitterionic peroxide occur.Accompanying drawing 1B shows this reaction process, and it expands to show the complexity of the intermediate that this decomposition method produces.
Although may have about seven kinds of intermediates (not computational geometry isomer), only have a pair of product formation, aldehyde and carboxyl ester aldehyde.Significantly, if this ozonolysis reactions is succeeded by the completing of oxidizing process, product is carboxylic acid and dicarboxylic acids (accompanying drawing 1C).
II. ozone decomposed
In a specific embodiment, the present invention is used in the O increasing in liquid solvent (that is, liquid medium) 3solubility provides for implementing improved method and the reaction condition of ozone decomposed.Should can comprise for implementing method and the reaction condition of ozone decomposed, by a kind of substantially with respect to O 3number and the amount of byproduct are not expected in the utilization that is the liquid solvent of inertia with restriction.This ozone decomposed method can be implemented, wherein, and O 3solubility in this liquid phase is for adjustable with pressure, so that the ability of control response speed and product selectivity to be provided.This method and reaction can be by being used liquid carbon dioxide (P c, CO 2=73.76bar; T c, CO 2=31.1 ℃ or 304.25K) or carbon dioxide expanded liquid as this solvent medium, realize.
In a specific embodiment, this ozone decomposed can be implemented with liquid carbon dioxide and different carbon dioxide expanded solvent liquids, for example, and natural unsaturated acids (for example, oleic acid) or its methyl esters.The reaction rate of ozone decomposed is probably because the low solubility of ozone in liquid phase limits.Carbon dioxide and carbon dioxide expanded liquid (CXLs) can improve O as the utilization of reaction medium 3solubility and the environment for ozone decomposed that an inertia is provided.In addition the carbon dioxide not firing, also can be as mixed mutually in n-hexane with low polar solvent.Should can produce carboxylic acid, dicarboxylic acids, terminal carboxyl group alcohol or carboxyl aldehyde succeeded by the ozone decomposed of suitable hydrolysis, reduction or an oxidation step.It should be noted that with other the aliphatic acid with two, three carbon-to-carbon double bonds and also can expect same result.
In a specific embodiment, ozone decomposed can be at liquid CO 2middle enforcement.Demonstrate O herein 3at liquid CO 2in be stable, substantially not with CO 2chemically reactive.Near ozone critical pressure, finely tune pressure and can adjust continuously O 3at liquid CO 2in solubility (for example, increase solubility reach about order of magnitude).For example,, for example, at-0.7 ℃ (272.45K) (, 1.044Tc, O 3), at 52.4bar (0.94Pc, O 3), O 3at liquid CO 2in solubility experiment be determined as about 0.006 absorbance unit, at 65.5bar (1.18Pc, O 3), it is 0.06 absorbance unit.Therefore, this sensitive O 3at liquid CO 2in solubility adjustment capability and O 3extreme compressibility in contiguous its critical point is relevant.
O 3contiguous its critical-temperature when-0.7 ℃ (272.45K) (, between 1-1.25Tc, O 3).Thereby for example, when pressure is increased and surpasses its critical pressure when (, surpassing about 55.6bar) by isothermal, ozone compressibility (with its density) will be increased sharply.On the other hand, as O 3the air of air-flow background gas and O 2, when-0.7 ℃ (272.45K), enough, away from critical-temperature separately, thus, in 50.6-66.9bar pressure range, there is the character of perfect gas, and in compressibility, do not show any increase sharply.Similarly, even O 3at air stream or at O 2in stream, occur diluted concentration, for example, at the order of magnitude of several mole percents, its compressibility, and density, sharply increase in contiguous its critical pressure, causes that it is dissolved in liquid CO selectively 2.This phenomenon is similar when its pressure increases over its critical pressure, near-critical CO 2in organic solvent, increase and dissolve.Other at CO 2or CO 2expanding liquid is as follows as the advantage that increases ozone concentration in solvent medium: (i) due to the dense CO as a kind of fire retardant in gas phase 2existence and reduce flammable dangerous; (ii) CO 2lower than most organic solvent toxicity; (iii) from environment, consider CO 2use be favourable, if it derives from existing but not chelating source; (iv) product can by decompression easily with CO 2separated.
Ozone decomposed medium for first step can be any liquid CO in the various temperature close to ozone critical-temperature 2.At liquid CO 2the temperature of middle ozone can, between the ozone Tc of 0.75 to 1.5 times, more preferably, at the ozone Tc of about 0.9 to about 1.35 times, most preferably arrive the ozone Tc of about 1.25 times about 0.95.Preferably at liquid CO 2the temperature of middle ozone can be about 1 times, the ozone Tc of about 1.1 times and about 1.15 times.This system of absolute unit (Kelvin or Lan Shi) expression for temperature as Tc function; Yet this temperature and temperature range can be converted into other unit.
Ozone decomposed medium for first step can be any in the temperature close to ozone critical-temperature with close to the liquid CO under the suitable pressure of critical pressure 2.Ozone is at liquid CO 2in pressure be the ozone Pc of 0.75 to 1.5 times, preferably the ozone Pc of approximately 0.9 to approximately 1.35 times, most preferably from about the ozone Pc of 0.95 to approximately 1.25 times.At liquid CO 2the pressure of middle ozone is preferably the ozone Pc of approximately 1 times, approximately 1.1 times and approximately 1.15 times.In other words, ozone is at liquid CO 2in pressure can be higher than about 40.5bar, approximately between 45.6bar and 76bar, more preferably at about 50.7bar to about 65.9bar, most preferably at about 54.7bar to about 60.8bar.Ozone is at liquid CO 2in pressure be preferably about 52.7bar, about 55.7bar and about 59.8bar.Pressure as Pc function can represent with atmospheric pressure (atm) or bar, other pressure unit's transformation of use that also can be suitable.
Ozone decomposed medium for first step can be any approaching and preferred various liquid CO 2s more than ozone critical density that have.The density of ozone is at 0.75 to 1000 ozone ρ cbetween, more preferably at approximately 0.9 to approximately 100 ozone ρ cbetween, most preferably at approximately 0.95 to approximately 10 ozone ρ c.
Ozonolysis reactions is heat release, and solvent can relax reaction rate, also or, the rate of heat production.Solvent, compare with substrate be inertia or inertia more, served as a kind of heat dump with absorption reaction heat.Yet, have multiple situation, wherein, when providing q.s when playing solvent action and providing enough substrate for ozonolysis reactions, substrate can also be solvent.
Ozone decomposed can be at liquid solvent as organic acid, alcohol, carrene, ethyl acetate, oxolane with even carry out in water; Yet they may produce a series of intermediate peroxide.Water is desirable, but this reaction sour for higher molecular weight and ester may need the application of two-phase liquid system.Alcohol due to its good solubility relation and partly because this solvent can reflect the alkyl of this ester but be attractive.Alcohol as solvent for the shortcoming of ozone decomposed is, their sensitiveness to oxidation, one may be dangerous factor.In the present invention, a kind of solvent system, as carbon dioxide expanded liquid (CXL), produces with low-molecular-weight alcohol, methyl alcohol and ethanol, can be used.
CXLs and the validity of other CXLs liquid fluxs in catalytic oxidation can utilize pure molecular oxygen to increase.Their advantage comprises O 2high-dissolvability (for example,, up to the more than 100 times of organic solvent) and domination gas phase and the security benefit of not firing medium of reaction medium in balancing each other.Except take the oxidant solubility increasing, be basic method strengthening, the molecular motion in CXLs and most of Media Ratio are also high.Further, take polarity alcohol is increasing reaction rate and apolar medium as postcritical CO as basic CXLs has shown polarity 2or the comparison of hydro carbons.
Methanol-based CXLs can be used as liquid medium for the oxidation cleavage of methyl oleate and those higher unsaturated acids methyl esters.Aliphatic acid is if palmitic acid is at methyl alcohol or supercritical CO 2middlely shown limited solubility.Even if reach at pressure under the condition of 150bar, palmitic acid is at supercritical CO 2in solubility be 10 -4the order of magnitude of molar fraction.For example, soya-bean oil also can be used as liquid medium for ozone decomposed.Work as CO 2while being released, emulsion disappears, and reproduce at methyl alcohol/soya-bean oil interface.This observation has represented to be dispersed in CO as emulsion 2the possibility of the fatty acid-based end in expansion methyl alcohol and then enforcement ozone decomposed.Therefore, carbon dioxide expanded methyl alcohol demonstrate be very suitable for terrifically unsaturated acids methyl esters ozone oxidation to produce the difunctional molecule of lower molecular weight, with as the importance of bio-refineries product.Yet our product demonstrates, O 3may corrode methyl alcohol, if particularly the concentration of methyl alcohol is substantially than the height of substrate.
The example that can be used to the solvent as CXL of ozone decomposed comprises: lighter hydrocarbons (C 4or lower) liquid, methyl alcohol, ethanol, low-carbon alcohols (for example, C 4-C 10), higher alcohols (for example, C 10-C 20), n-hexane, SF 6, xenon, water, the aqueous solution, fluorocarbon solvent, high oxidation molecule, highly fluorinated molecule, CF 3cO 2h, ionic liquid, strong liquid acid, H 2sO 4, HSO 3f, HSO 3cF 3, organic acid, saturated hydrocarbons, for the Liquid substrate of ozone decomposed and combination thereof etc.The solubility of ozone in any above-mentioned solvent can increase by preparation as CXL described herein.
In some cases, the solvent in a kind of CXL is inertia preferably.The possible example as atent solvent in CXL that can be used to ozone decomposed comprises: SF 6, xenon, water, the aqueous solution, fluorocarbon solvent, high oxidation molecule, highly fluorinated molecule, CF 3cO 2h, H 2sO 4, HSO 3f and HSO 3cF 3.
Test shows, the solvent of some non-inertia can be used, if O 3on solvent, corrode selectively substrate (like this situation is exactly when using methyl alcohol as solvent additive).That is, in predetermined substrate of reacting, have more in reactive situation, Liquid substrate can be used as solvent for ozone decomposed.This allow ozone to react with intended substrate but not with solvent reaction (for example, possible be used in inertia or the more substrate in the solvent of inertia).For example, some choice of the substrates things, as the vegetable oil that comprises soya-bean oil, its known can with ozone reaction, when comparatively speaking intended substrate has more reactivity, can be used as solvent.Here solvent is the component that has more inertia in solvent-base system.Therefore, this solvent is completely or substantially ozone is corroded is the liquid of inertia, or still less preferentially by ozone, is corroded a kind of having more under reactive substrate existence.
The example that can be used to the solvent as the non-inertia of CXL of ozone decomposed comprises: methyl alcohol, ethanol, low-carbon alcohols (for example, C 4-C 10), higher alcohols (for example, C 10-C 20), n-hexane, ionic liquid, liquid acid, organic acid and saturated hydrocarbons.
In a specific embodiment, ozone decomposed method of the present invention can be used to oil & fat as the oxicracking of unrighted acid.Two keys of unrighted acid are provided for implementing the reactive site of various conversions.Correspondingly, the oxidation scission of alkene can be obtained by ozone decomposed.As shown in Figure 2 A, an ozonide of this initial formation of high selectivity reaction, it can continue to produce aldehyde or carboxylic acid, adopts respectively the method for reduction or oxidation.The method is attractive especially for producing the carboxylic acid that comprises odd numbers of carbon atoms on polymethylene main chain.For example, industrial, azelaic acid is produced by ozone decomposed by oleic acid, and is used in the manufacture of plasticizer, lubricant, hydraulic pressure finish and cosmetics.It is also used as an antiseptic on acne treatment.The potential substrate for ozonolysis reactions is widely, comprises aliphatic acid, their ester and the source of other oil & fats.
In a specific embodiment, this ozone decomposed method can be used to prepare batching and the reagent of perfume and flavor chemistry.For example, the ozonisation of terpenes can be used for preparation batching and reagent.Oxidized compound forms the major part of most of aromatics (odiferouschemistry), no wonder the ozone decomposed cracking of alkene is widely used in perfume and perfume industry.From the production of the distinct fragrance molecule of terpenes, with the ozone decomposed of a pi-allyl part in terpenes molecule, be cracked into starting point with most of synthetic routes and exist chemistry widely and contact.For example, the ozone decomposed of terpenes, can form (-)-3-isopropyl-6-containing oxygen enanthaldehyde (oxoheptanal) by reducing process to menthene ((+)-p-menth-1-ene).Then this molecule can experience various reactions for example, to form some aromatic molecules (, new mown hay, icy, the lily of the valley, class bergamot, rose/orange blossom etc.), as shown in Figure 2 B.
In a specific embodiment, this ozone decomposed method can be used to for the preparation of the activator of medicament or for forming the reagent of medicinal product.Suitably substrate is as the ozone decomposed of natural products or physiological activator reagent, can be used for preparing the derivative of new physiological activator reagent or various biologically active molecules.For example, anavar is an anabolic steroid for promoting to increase through having the patient body weight of operation, chronic infection or severe trauma all through the ages.It also alleviates the ostalgia relevant with osteoporosis.Its initial Shi You G.D.Searle company finds, from methyl androstane alkanol ketone by using high toxicity OsO a kind of comprising 4and Pb (OAc) 4multistage route synthetic.A kind of alternative route for the preparation of several kilograms of USP anavars is studied successfully by Cedarburg pharmaceutical companies, it utilizes an ozonolysis reactions to produce a kind of key intermediate acid with superior returns, and has avoided using and problem that the accumulation of this harmful waste brings of highly toxic, persistence reagent.As shown in Figure 2 C, ozone decomposed method of the present invention can be used for preparing anavar with a kind of safer, more economical method.
In another embodiment, ozone decomposed method of the present invention can be used for preparing antibiotic from suitable substrate, as cefaclor and Ceftibuten.Cefaclor and Ceftibuten are the compounds that belongs to so-called cephalosporin antibiotics medicine one class.They are effectively to various infection, and it is found by Shionogi and Japanese Osaka Co., Ltd.They are synthetic from penicillin sulfoxide at first, but the production that the scientist of Schering Plough research institute attempt reduces costs has caused the synthetic route from cephalosporin culture medium (broths).In this route, a committed step is ozone decomposed step, and it is transformed into 3-hydroxy cephem (2) by 3-exomethylenecepham rhzomorph (1).As shown in Figure 2 D, ozone decomposed method of the present invention can be used for preparing 3-hydroxy cephem (2) with a kind of safer, more economical method.
In another embodiment, ozone decomposed method of the present invention can be used for preparing 2-hydroxyl indane-2-formaldehyde (2-Hydroxyindan-2-carboxaldehyde).Pfizer has developed a kind of synthetic method of several kilograms of scales for 2-hydroxyl indane-2-formaldehyde and 2-indenone derived aldehydes previously, and it is used in a reductive amination process.One of 2-indenone experience adopts Ge Shi (grignard) addition of vinyl magnesium bromide to produce a kind of tertiary allyl alcohol.It has experienced the ozone decomposed in methyl alcohol, and this solvent is traped this triiron tetroxide intermediate to form methoxyl group-hydroperoxides subsequently.These hydroperoxides by with bisulfite sodium reduction to form a kind of stable bisulfite adduct, it is better than this aldehyde and is used in reduction amination.As shown in Figure 2 E, ozone decomposed method of the present invention can be used for preparing 2-hydroxyl indane-2-formaldehyde with a kind of safer, more economical method.
In a specific embodiment, ozone decomposed method of the present invention can be used for non-olefinic oxidation reaction.For example, non-olefinic oxidation reaction can be that benzyl substrate etc. is by the oxidation of ozone decomposed.Correspondingly, the ozone decomposed chemical property of organic matter substrate is not limited to the selective splitting of this pair of key.Show, use a kind of transition-metal catalyst, ozone can be oxidized the benzyl compounds of replacement effectively to form their corresponding benzaldehydes and stupid formic acid.Similarly, solvent described herein and reaction condition and use manganese (II) acetate are as catalyst, and the oxidation of toluene derivative can cause the formation of aldehyde or carboxylic acid product.The unique tail gas producing is oxygen.Ozone decomposed method of the present invention can be used for preparing benzaldehyde and stupid formic acid with a kind of safer, more economical method.
In a specific embodiment, ozone decomposed method of the present invention can be used for the production of singlet oxygen.The singlet oxygen of producing from ozone has obtained some concerns recently.Traditional production method is included in a kind of emulsion as irradiated oxygen with ultraviolet ray under the condition of four benzene porphin beautiful jades existence.The existence of a large amount of dioxygens, organic solvent and light, adds and has stoped the cost of special gas/liquid photoreaction device its commercial Application, and its industrial use is limited in small-scale spices and perfume production application.Therefore, produce 1o 2unglazed method be extensively studied, adopting molybdate is the most attractive by hydrogen peroxide catalyzed conversion.Ozone can also be for the production of 1o 2, showing, 1,1 '-bis-(diphenylphosphine) ferrocene has promoted the division of ozone to produce 1o 2.Correspondingly, ozone has the CO of 1,1 '-bis-(diphenylphosphine) ferrocene 2or in CXL, can be used for producing 1o 2.In addition, (for example, hydrogenation) reclaimed in the reduction of the ferrocene catalyst by this oxidised form, and a kind of technique of serialization can be used for producing 1o 2.
In a specific embodiment, ozone decomposed method of the present invention can be used for the oxidation of methane.Ozone is at CO 2or the solubility strengthening in CXL can be used for methane by the oxidation of ozone decomposed.Previously, the oxidation of methane it is reported it is methane conversion to be become to protonated formaldehyde in super acids medium.In this powerful acid solution, to have reported, methane is oxidized, simultaneously with oligomeric, forms protonated acetone or relevant alkyl carbonium ion.Present this conversion can be with ozone at CO 2or implement in CXL.
Ozone decomposed method of the present invention can be used for multiple substrate.Most of general substrates can be vegetablefats acid, fatty acid ester, fat and oily.The group that the freely following material of example choosing of vegetablefats acid forms: butyric acid, caproic acid, sad, capric acid, laurate, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, cerinic acid, octacosanoic acid, triacontanoic acid, with positive lacceroic acid, and there is odd numbers of carbon atoms, as propionic acid, positive valeric acid, enanthic acid, n-nonanoic acid, undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosoic acid, tricosanic acid, neocerotic acid, carboceric acid, isobutyric acid, isocaproic acid, isooctyl acid, isodecyl acid, different month silicic acid, 11-methyl moon silicic acid, different myristic acid, 13-Methyl Tetradecanoic Acid, different hexadecylic acid, 15-methyl palmitic acid, isostearic acid, 17-methyl stearic acid, different arachidic acid, 20 acid of 19-methyl, α--thylhexoic acid, α-hexyldecanoic acid, α-heptyl undecanoic acid, 2-decyl tetradecylic acid, 2-hendecyl tetradecylic acid, 2-decyl pentadecanoic acid, 2-hendecyl pentadecanoic acid, isostearic acid (Fine oxocol 1800acid) (daily output chemical industry Co., Ltd product), 6-Methyloctanoic Acid, 8-methyl capric acid, 10-methyl dodecoic acid, 12-methyl tetradecylic acid, 14-methyl palmitic acid, 16 methyl stearic acid, 20 acid of 18-methyl, 20-methyl behenic acid, 22-methyl tetracosanoic acid, 24-methyl cerinic acid, 26-methyl stearic acid, comprise 4-nonene bisgallic acid, decylenic acid, 4-lauroleic acid, linderic acid, lauroleic acid, 4 tetradecenoic acids, physeteric acid, 9-tetradecenoic acid, palmitoleic acid, petroselinic acid, oleic acid, 9-octadecenoic acid, vaccenic acid, 9-eicosenoic acid, cis-11-eicosenoic acid, docosenoic acid, 13-erucic acid, 15-tetracosenoic acid, 17-hexacosenoic acid, 6,9,12,15-, 16 carbon tetraenoic acids, linoleic acid, leukotrienes (18:3 n3), acid and gamma-linolenic (18:3 n6), the trans-11 trans-13-octatecatrienoic acids of cis-9-, gaducene acid (20:1), the trans-11 trans-13-octatecatrienoic acids of cis-9-, punicic acid, stearidonic acid, parinaric acid, Arachidonic Acid, erucic acid, EPA (EPA), DPA, DHA (DHA), Alpha-hydroxy laurate, Alpha-hydroxy myristic acid, Alpha-hydroxy palmitic acid, Alpha-hydroxy stearic acid, ω-hydroxylauric acid, Alpha-hydroxy arachidic acid, 9-hydroxyl-12-octadecenoic acid, ricinoleic acid, Alpha-hydroxy behenic acid, 9-hydroxyl-trans-10,12-octadecadienoic acid, noise made in coughing or vomiting Lay Buddhist nun acid (kamolenic acid), 3,11-ipurolic acid, DHSA, 12-hydroxy stearic acid, oxalic acid, citric acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, D, L MALIC ACID, and derivative or any combination.
The freely group of following Physical Capital Stock of example choosing of fatty acid ester: methyl laurate, methyl myristate, methyl hexadecanoate, methyl oleate, methyl elaidate ester, methyl linoleate, methyl linolenate, methyl stearate, methyl eruciate, methyl ricinoleate, methyl Linolenic Acid, 11,13 triolefins-4-keto ester, Linolenic Acid, 11,13 triolefins-4-keto ester, methyl eleostearate, methyl arachidonate, methyl clupanodonic acid ester, ethyl laurate, acetate, ethyl palmitate, ethyl oleate, ethyl elaidic acid ester, ethyl linoleate, ethyl linolenic acid ester, ethyl stearte, ethyl erucate, ethyl ricinoleate, ethyl Linolenic Acid, 11,13 triolefins-4-keto ester, ethyl eleostearate, ethyl arachidonate, ethyl clupanodonic acid ester, propyl group laurate, propyl group myristinate, propyl group palmitate, propyl group oleate, propyl group elaidic acid ester, propyl group linoleate, propyl group linolenate, propyl group stearate, propyl group eruciate, propyl group ricinoleate, propyl group Linolenic Acid, 11,13 triolefins-4-keto ester, propyl group eleostearate, propyl group arachidonate, propyl group clupanodonic acid ester, isopropyl laruate, isopropyl myristate, isopropyl palmitate, acid isopropyl, isopropyl elaidic acid ester, isopropyl linoleate, isopropyl linolenate, Emerest 2310, isopropyl eruciate, isopropyl ricinoleate, isopropyl Linolenic Acid, 11,13 triolefins-4-keto ester, isopropyl eleostearate, isopropyl arachidonate, isopropyl clupanodonic acid ester, butyl laurate, butyl myristate, butyl palmitate, butyl oleate, butyl elaidic acid ester, butyl linoleate, butyl linolenate, butyl stearate, butyl eruciate, butyl ricinoleate, butyl Linolenic Acid, 11,13 triolefins-4-keto ester, butyl eleostearate, butyl arachidonate, butyl clupanodonic acid ester, sec-butyl laurate, sec-butyl myristate, sec-butyl palmitate, secondary butyl oleate, sec-butyl elaidic acid ester, sec-butyl linoleate, sec-butyl linolenate, sec-butyl stearate, sec-butyl eruciate, sec-butyl ricinoleate ester, sec-butyl Linolenic Acid, 11,13 triolefins-4-keto ester, sec-butyl eleostearate, sec-butyl arachidonate, sec-butyl clupanodonic acid ester, isobutyl group laurate, isobutyl group myristate, isobutyl palmitate, tebelon, isobutyl group elaidic acid ester, isobutyl group linoleate, isobutyl group linolenate, isobutyl stearate, isobutyl group eruciate, isobutyl ricinoleate, isobutyl group Linolenic Acid, 11,13 triolefins-4-keto ester, isobutyl group eleostearate, isopropyl arachidonate, isobutyl group clupanodonic acid ester, amyl laurate, amyl group myristate, amyl group palmitate, amyl oleate, amyl group elaidic acid ester, amyl group linoleate, amyl group linolenate, amyl stearate, amyl group eruciate, amyl group ricinoleate ester, amyl group Linolenic Acid, 11,13 triolefins-4-keto ester, amyl group eleostearate, amyl group arachidonate, amyl group clupanodonic acid ester, hexyl laurate fat, hexyl myristate, hexyl palmitate, hexyl oleate, hexyl elaidic acid ester,Hexyl linoleate, hexyl linolenate, hexyl stearate, hexyl eruciate, hexyl ricinate, hexyl Linolenic Acid, 11,13 triolefins-4-keto ester, hexyl eleostearate, hexyl arachidonate, hexyl clupanodonic acid ester, heptyl laurate, heptyl myristate, heptyl palmitate, heptyl oleate, heptyl elaidic acid ester, heptyl linoleate, heptyl linolenate, heptyl stearate, heptyl eruciate, heptyl ricinoleate ester, heptyl Linolenic Acid, 11,13 triolefins-4-keto ester, heptyl eleostearate, heptyl arachidonate, heptyl clupanodonic acid ester, octyl group laurate, octyl group myristinate, octyl palmitate, octoil acid esters, octyl group elaidic acid ester, octyl group linoleate, octyl group linolenate, octyl stearate, octyl group eruciate, octyl group ricinoleate ester, octyl group Linolenic Acid, 11,13 triolefins-4-keto ester, octyl group eleostearate, octyl group arachidonate, octyl group clupanodonic acid ester, 2-ethylhexyl laurate, 2-ethylhexyl myristate, 2-ethyl hexyl palmitat, 2-ethylhexyl oleate, 2-ethylhexyl elaidic acid, 2-ethylhexyl linoleate, 2-ethylhexyl linolenate, 2-ethylhexyl stearate, 2-ethylhexyl eruciate, 2-ethylhexyl ricinoleate ester, 2-ethylhexyl Linolenic Acid, 11,13 triolefins-4-keto ester, 2-ethylhexyl eleostearate, 2-ethylhexyl arachidonate, 2-ethylhexyl clupanodonic acid ester, the laurate tert-butyl ester, the myristic acid tert-butyl ester, the palmitic acid tert-butyl ester, the oleic acid tert-butyl ester, tert-butyl group elaidic acid ester, tert-butyl group linoleate, tert-butyl group linolenate, the stearic acid tert-butyl ester, tert-butyl group eruciate, the ricinoleic acid tert-butyl ester, tert-butyl group Linolenic Acid, 11,13 triolefins-4-keto ester, tert-butyl group eleostearate, tert-butyl group arachidonate, tert-butyl group clupanodonic acid ester, iso-octyl laurate, iso-octyl myristate, isobutyl palmitate, iso-octyl oleate, iso-octyl elaidic acid ester, iso-octyl linoleate, iso-octyl linolenate, iso-octyl stearate, iso-octyl eruciate, iso-octyl ricinate, iso-octyl Linolenic Acid, 11,13 triolefins-4-keto ester, iso-octyl eleostearate, iso-octyl arachidonate, iso-octyl clupanodonic acid ester, nonyl laurate, nonyl myristate, nonyl palmitate, nonyl oleate, nonyl elaidic acid ester, nonyl linoleate, nonyl linolenate, nonyl stearate, nonyl eruciate, nonyl ricinoleate, nonyl Linolenic Acid, 11,13 triolefins-4-keto ester, nonyl eleostearate, nonyl arachidonate, nonyl clupanodonic acid ester, decyl laurate, decyl myristate, decyl palmitate, Ceraphyl 140, decyl elaidic acid ester, decyl linoleate, decyl linolenate, decyl stearate, decyl eruciate, decyl ricinoleate, decyl Linolenic Acid, 11,13 triolefins-4-keto ester, decyl eleostearate, decyl arachidonate, decyl clupanodonic acid ester, hendecyl laurate, hendecyl myristate, hendecyl palmitate, hendecyl oleate, hendecyl elaidic acid ester,Hendecyl linoleate, hendecyl linolenate, hendecyl stearate, hendecyl eruciate, hendecyl ricinoleate, hendecyl Linolenic Acid, 11,13 triolefins-4-keto ester, hendecyl eleostearate, hendecyl arachidonate, hendecyl clupanodonic acid ester, dodecyl laurate, dodecyl myristate, dodecyl palmitate, dodecyl oleate, dodecyl elaidic acid ester, dodecyl linoleate, dodecyl linolenate, dodecyl stearate, dodecyl eruciate, dodecyl ricinoleate, dodecyl Linolenic Acid, 11,13 triolefins-4-keto ester, dodecyl eleostearate, dodecyl arachidonate, dodecyl clupanodonic acid ester, methyl brasileic acid ester, ethyl brasileic acid ester, propyl group brasileic acid ester, isopropyl brasileic acid ester, butyl brasileic acid ester, sec-butyl brasileic acid ester, isobutyl group brasileic acid ester, tert-butyl group brasileic acid ester, amyl group brasileic acid ester, acid esters is strangled by hexyl Brazil, heptyl brasileic acid ester, octyl group brasileic acid ester, 2-ethylhexyl brasileic acid ester, iso-octyl brasileic acid ester, nonyl brasileic acid ester, decyl brasileic acid ester, hendecyl brasileic acid ester, dodecyl brasileic acid ester, ethoxy laurate, ethoxy myristate, ethoxy palmitate, ethoxy oleate, ethoxy elaidic acid ester, ethoxy linoleate, ethoxy linolenate, ethoxy stearate, ethoxy eruciate, ethoxy ricinoleate ester, ethoxy Linolenic Acid, 11,13 triolefins-4-keto ester, ethoxy eleostearate, ethoxy arachidonate, ethoxy clupanodonic acid ester, ethoxy brasileic acid ester, polyethoxy laurate, polyethoxy myristic acid, polyethoxy palmitic acid, polyethoxy oleic acid, polyethoxy elaidic acid, polyethoxy linoleic acid, polyethoxy leukotrienes, polyethoxy stearic acid, polyethoxy erucic acid, Cremaphor EL acid, polyethoxy Linolenic Acid, 11,13 triolefins-4-ketone acid, polyethoxy eleostearic acid, polyethoxy arachidonic acid, polyethoxy clupanodonic acid, polyethoxy brasileic acid, hydroxypropyl laurate, hydroxypropyl myristate, hydroxypropyl palmitate, hydroxypropyl oleate, hydroxypropyl elaidic acid ester, hydroxypropyl linoleate, hydroxypropyl linolenate, hydroxypropyl stearate, hydroxypropyl eruciate, hydroxypropyl ricinoleate ester, hydroxypropyl Linolenic Acid, 11,13 triolefins-4-keto ester, hydroxypropyl eleostearate, hydroxypropyl arachidonate, hydroxypropyl clupanodonic acid ester, hydroxypropyl brasileic acid ester, poly-propoxyl group laurate, poly-propoxyl group myristic acid, poly-propoxyl group palmitic acid, poly-propoxylated oleic acid, poly-propoxyl group elaidic acid, poly-propoxyl group linoleic acid, poly-propoxyl group leukotrienes, poly-propoxyl group stearic acid, poly-propoxyl group erucic acid, poly-propoxyl group castor oil acid, poly-propoxyl group Linolenic Acid, 11,13 triolefins-4-ketone acid, poly-propoxyl group eleostearic acid, poly-propoxyl group arachidonic acid, poly-propoxyl group clupanodonic acid, poly-propoxyl group brasileic acid, cyclopenta laurate, cyclopenta myristate, cyclopenta palmitate, cyclopenta oleate, cyclopenta elaidic acid ester, cyclopenta linoleate, cyclopenta linolenate, cyclopenta stearate, cyclopenta eruciate, cyclopenta ricinoleate ester,Cyclopenta Linolenic Acid, 11,13 triolefins-4-keto ester, cyclopenta eleostearate, cyclopenta arachidonate, cyclopenta clupanodonic acid ester, cyclopenta brasileic acid ester, cyclohexyl laurate, cyclohexyl myristate, cyclohexyl palmitate, cyclohexyl oleate, cyclohexyl elaidic acid ester, CHLA ester, cyclohexyl linolenate, cyclohexyl stearate, cyclohexyl eruciate, cyclohexyl ricinoleate ester, cyclohexyl Linolenic Acid, 11,13 triolefins-4-keto ester, cyclohexyl eleostearate, cyclohexyl arachidonate, cyclohexyl clupanodonic acid ester, cyclohexyl brasileic acid ester, methoxy ethyl laurate, methoxy ethyl myristate, methoxy ethyl palmitate, methoxy ethyl oleate, methoxy ethyl elaidic acid ester, methoxy ethyl linoleate, methoxy ethyl linolenate, methoxy ethyl stearate, methoxy ethyl eruciate, methoxy ethyl ricinoleate ester, methoxy ethyl Linolenic Acid, 11,13 triolefins-4-keto ester, methoxy ethyl eleostearate, methoxy ethyl arachidonate, methoxy ethyl clupanodonic acid ester, methoxy ethyl brasileic acid ester, isopropoxyethyl laurate, isopropoxyethyl myristate, isopropoxyethyl palmitate, isopropoxyethyl oleate, isopropoxyethyl elaidic acid ester, isopropoxyethyl linoleate, isopropoxyethyl linolenate, isopropoxyethyl stearate, isopropoxyethyl eruciate, isopropoxyethyl ricinoleate ester, isopropoxyethyl Linolenic Acid, 11,13 triolefins-4-keto ester, isopropoxyethyl eleostearate, isopropoxyethyl arachidonate, isopropoxyethyl clupanodonic acid ester, isopropoxyethyl brasileic acid ester, butoxyethyl group laurate, butoxyethyl group myristate, butoxyethyl group palmitate, butoxyethyl group oleate, butoxyethyl group elaidic acid ester, butoxyethyl group linoleate, butoxyethyl group linolenate, butoxyethyl stearate, butoxyethyl group eruciate, butoxyethyl group eleostearate, butoxyethyl group Linolenic Acid, 11,13 triolefins-4-keto ester, butoxyethyl group ricinoleate ester, butoxyethyl group arachidonate, butoxyethyl group clupanodonic acid ester, butoxyethyl group brasileic acid ester, methoxy-propyl laurate, methoxy-propyl myristate, methoxy-propyl palmitate, methoxy-propyl oleate, methoxy-propyl elaidic acid ester, methoxy-propyl linoleate, methoxy-propyl linolenate, methoxy-propyl stearate, methoxy-propyl eruciate, methoxy-propyl ricinoleate ester, methoxy-propyl Linolenic Acid, 11,13 triolefins-4-keto ester, methoxy-propyl eleostearate, methoxy-propyl arachidonate, methoxy-propyl clupanodonic acid ester, methoxy-propyl brasileic acid ester, ethoxycarbonyl propyl laurate, ethoxycarbonyl propyl myristate, ethoxycarbonyl propyl palmitate, ethoxycarbonyl propyl oleate, ethoxycarbonyl propyl elaidic acid ester, ethoxycarbonyl propyl linoleate, ethoxycarbonyl propyl linolenate, ethoxycarbonyl propyl stearate, ethoxycarbonyl propyl eruciate, ethoxycarbonyl propyl ricinoleate ester, ethoxycarbonyl propyl Linolenic Acid, 11,13 triolefins-4-keto ester, ethoxycarbonyl propyl eleostearate, ethoxycarbonyl propyl arachidonate, ethoxycarbonyl propyl clupanodonic acid ester, ethoxycarbonyl propyl brasileic acid ester, butoxypropyl laurate, butoxypropyl myristate, butoxypropyl palmitate, butoxypropyl oleate, butoxypropyl elaidic acid ester, butoxypropyl linoleate, butoxypropyl linolenate, butoxypropyl stearate, butoxypropyl eruciate, butoxypropyl ricinoleate ester, butoxypropyl Linolenic Acid, 11,13 triolefins-4-keto ester, butoxypropyl eleostearate, butoxypropyl arachidonate, butoxypropyl clupanodonic acid ester, butoxypropyl brasileic acid ester, isopropoxide propyl laurate, isopropoxide propyl myristate, isopropoxide propyl palmitate, isopropoxide propyl oleate, isopropoxide propyl elaidic acid ester, isopropoxide propyl linoleate, isopropoxide propyl linolenate, isopropoxide propyl stearate, isopropoxide propyl eruciate, isopropoxide propyl ricinoleate ester, isopropoxide propyl Linolenic Acid, 11,13 triolefins-4-keto ester, isopropoxide propyl eleostearate, isopropoxide propyl arachidonate, isopropoxide propyl clupanodonic acid ester, isopropoxide propyl brasileic acid ester, etc.
The example of grease is selected from the group that following material forms: animal tallow, tallow, borneo tallow, butterfat, cameline oil, candle fish oil, corn oil, castor oil, cocoa butter, cocoa butter substituent, coconut oil, cod-liver oil, coriander oil, corn oil, cotton seed oil, linseed oil, hazelnut oil, hemp-seed oil, herring oil, mist ice grass grease, curcas oil, candlenut oil, lanolin, lard, linseed oil, mango kernel oil, sea oil, Bai Manghua seed oil, pilchardine, butterfat, mowrah fat, mustard oil, suet, hoof oil, olive oil, the orange fin salmon oil that connects, palm oil, palm-kernel oil, palm-kernel oil acid glyceride, palm kernel tristerin, palmitoleic acid glyceride, glyceryl palmitostearate, peanut oil, general vara butter (phulwara butter), heap beast oil, rapeseed oil, rice bran oil, safflower oil, sal fat, pilchard oil, oil tea oil, thank to her fat, sher butter, soya-bean oil, sunflower seed oil, pine tar, tallow, Chinese toon oil, tung oil, vegetable oil, whale oil, triglycerides, diglyceride, monoglyceride, olein, MCT Oil, and derivative, conjugate derivative, genetically altered derivative and mixture.Other source of suitable fat acid comprises with the cooking oil of crossing, the oil slick of waste water treatment plant, animal tallow are less than 15% animal or plant oil and fat and white grease, mainly take from the good grease of refining of pork and/or other animal tallow as tallow and pork lard, crude oil, " yellow grease ", free fatty acid content that used or that those preparations or cooking food produce when preparing food for restaurant or other food mechanism of human consumption.
In a specific embodiment, for the substrate of ozone decomposed at liquid CO 2in be soluble or substantially soluble or suspend.Some examples can comprise the compound of propylene, 1-butylene, cyclopentene, cyclohexene, cycloheptene, cyclo-octene, cis-1-2-talan, trans-stilbene and same type.
Yet the substrate that some expectations are reacted by ozone decomposed may be insoluble in carbon dioxide or carbon dioxide expanded liquid.This immiscible liquid is common in industrial process.In the case, interfacial surface area can be increased to overcome mass transfer limit, thereby improves reaction rate.Interfacial surface area can be by increasing with the strong stirring of mechanical agitator or ultrasonic wave mixing apparatus, two emulsion or dispersions of all manufacturing a kind of substrate in solvent phase.Other strong stirring method also can be for increasing the surface area at this interface.Therefore, the present invention can be used to substrate not exclusively soluble reaction in solvent.This is specially adapted to comprise the very multi-component important substrate from living resources of multiple bio oil described herein.
III. catalysis
As shown in Figure 1A and 1B, the product that reacts to obtain a kind of expectation with this substrate can occur in two steps.The first step is at CO 2or CO 2ozone decomposed in expanding liquid (being CXL), as described herein.The second step of overall process can be catalysis or the stoichiometry that relies on concrete development.For example, according to reports, the hydrolysis of three butyl oxide links (trioxolane) will produce corresponding dihydroxylated acid, and hydrolysis will produce aldehyde in the situation that gentle reducing agent exists.The detection display of balanced reaction formula, makes three butyl oxide links will produce the ketone/aldehyde of one mole and the carboxylic acid of a mole in the simple state of oxidation.In fact, between this three butyl oxide links burst times, when oxicracking by produce two moles carboxylic acid time, gentle reduction all converts two parts of generation to aldehyde.Strong reduction is by the alcohol that produces two moles.Therefore, new catalysis process can be used to ozone decomposed or unsaturated acids and their ester group and change into second step useful, lower molecular weight products in ozone.
In a specific embodiment, first and/or second step of this ozone decomposed method can be implemented with a kind of catalysis system.In common reaction, particularly in the cracking of carbon-to-carbon double bond, known catalysis system is not effective in the utilization that promotes ozone complete oxidation ability.Adopt a kind of transition-metal catalyst can relax the oxidation power of ozone in the catalysis of initial oxidation process.Catalyst relaxes ozone conventionally in two ways: by elimination, arrive the mechanical passage of ozone molecule, and the apparent conversion that changes into hydroxyl due to ozone adds reactor product still less, the selective disappearance of oxidant and the generation of desired product reduce.In the situation that lacking catalyst, ozone is transformed into metastable intermediate, 1,2 by carbon-to-carbon double bond group, 4-tri-butyl oxide links, it is applicable to the second step (solvolysis, oxidation, reduction) of the expection product series that causes a kind of easy selection that efficiency is high.Yet, the catalysis hope in second step, 1,2,4-ozonide changes into expection product, can improve by catalysis, no matter it is oxidation or reduction.Correspondingly.Catalyst can be used at CO 2with the ozone decomposed of substrate in CXLs, as described herein.The example of catalysis can comprise: take that to use transition metal ions be target as catalyst, iron (III) oxide, iron, cobalt, nickel, copper, manganese, chromium, manganese (for example, Mn (III) but not Mn (VII)), osmium, ruthenium and rhenium, manganoporphyrin, the poly-oxometallate of manganese central authorities, titanium, TiO 2, and combination, oxide etc.
IV. ozone purifying
In addition, the invention provides method and the reaction condition for the preparation of ozone or increase ozone purity.Ozone may be present in a kind of gas as in air or oxygen or can be from wherein separated.In the prior art, ozone is generated as called optical imaging.Ozone is often with producing its gas.Now, ozone can be by purifying from this original gas selectively.
In a specific embodiment, at CO 2or under the condition that exists of CXL, ozone can one close to the temperature of ozone Tc under the separation from oxygen or air by the pressure of increase system.That is to say, at CO 2or the same terms that increases ozone concentration in CXL can be used to the ozone of purifying from gas.Same, under the condition in ozone existence and without substrate, a temperature close to Tc, CO 2or CXL composition can be conditioned by increasing pressure.The shortage of substrate allows O 3from a kind of O 2+ O 3or a kind of O 3in+air draught, pass through at this CO 2or CXL in concentrated and separated, there is no reaction and the cracking of ozone.This separation process can be passed through at O 3following cooling this O of critical-temperature (for example ,-12 ℃ or 261.15K) 2/ air+O 3mixture and implement with by simple this system pressure that increases (for example,, close to O 3tens bar of critical pressure) by O 3freeze-out.The method is compared the separated O of Refrigeration Technique 3relatively more cheap and easy.
At CO 2or after the increase of the ozone concentration in CXL, all not gas in liquid can be removed.Ozone gas physical efficiency in liquid is therefore separated to obtain purifying ozone from this liquid.
In a specific embodiment, temperature is about 1 to about 1.2 times of ozone critical-temperatures, wherein, and system of absolute unit temperature for (Kelvin or Lan Shi) expression.
In a specific embodiment, pressure is increased to about 0.5 to about 2 times of ozone critical pressures.
In a specific embodiment, the ozone concentration in liquid is added to about order of magnitude.
In a specific embodiment, a kind of for extract the method for ozone from gas, the method comprises: about 0.8, at the temperature of about 1.5 times of ozone critical-temperatures, provide a kind of gas that contains ozone; Isothermal increases the pressure of this ozone to about 0.3 to about 5 times of ozone critical pressures; The ozone of this compression is introduced to a kind of liquid, and wherein, this liquid and combined with ozone thing have about 0.8 to the temperature of about 1.5 times of ozone critical-temperatures, and the pressure of this liquid and combined with ozone thing is about 0.3 to about 5 times of ozone critical pressures.Temperature is about 1 to about 1.2 times of ozone critical-temperatures, wherein, and system of absolute unit temperature for (Kelvin or Lan Shi) expression.Pressure is increased to about 0.5 to about 2 times of ozone critical pressures.Ozone concentration in liquid is increased at least about 5 times.This method can comprise provides ultrasonic wave to stir to this liquid and ozone.Ozone concentration in liquid is added to about order of magnitude.This liquid comprises liquid carbon dioxide, lighter hydrocarbons (C 4or lower), methyl alcohol, ethanol, alcohols, hexane, SF 6, xenon, water, fluorocarbon solvent, high oxidation molecule, highly fluorinated molecule, CF 3cO 2h, ionic liquid, strong liquid acid, H 2sO 4, HSO 3f, HSO 3cF 3, organic acid, saturated hydrocarbons or its composition.
In a specific embodiment, liquid is a kind of lighter hydrocarbons (C that comprises 4or lower), methyl alcohol, ethanol, alcohols, hexane, SF 6, xenon, water, fluorocarbon solvent, high oxidation molecule, highly fluorinated molecule, CF 3cO 2h, ionic liquid, strong liquid acid, H 2sO 4, HSO 3f, HSO 3cF 3, organic acid, saturated hydrocarbons or its composition carbon dioxide expanded liquid.
Test
1. ozone concentration measurement and ozone decomposed test are by being used a 10cm 3titanium high pressure observation unit is implemented.A sketch map of this reactor assembly 10 is shown in Figure 3.Reactor assembly 10 comprises a reaction under high pressure unit 12, and it has cylindrical or other profile.12 two ends, this unit have observation window 14 as sky blue window, and this is polyether-ether-ketone (PEEK) O RunddichtringO and the sealing of nut (not shown) for two ends.A spectrophotometer (not shown) (for example, marine optics optical fiber ultraviolet ray/visible spectrophotometer) is for measuring ultraviolet ray/visible spectrum by this sky blue window 14.The housing of unit 12 have one for 16, one, the mouth of ozone input for CO 2and/or 18, one 20, one mouths 24 for pressure sensor 26 inputs of mouth for thermocouple 22 inputs of the mouth of CXL input, an and mouth 28 for security rupture pressure disc 30.Ozone input 16 can have a titanium glass raw material (not shown) to guarantee good the mixing of ozone and these unit 12 inclusions.Sample can take out by any one mouthful from liquid phase or gas phase.Mixing is by being used a magnetic stirrer rod (not shown) to implement, and temperature regulates by using a circulation of fluid thermal jacket (not shown) contacting with this unit 12 to carry out.Temperature detects with thermocouple 22, and controls and record by a computer-controlled data collecting system 32 (Dasylab, measX GmbH & Co.KG).Data collecting system 32 control and the records that pressure detects with pressure sensor 26 and computerizeds control.
Ozone for example, by ozone generator 34 (, a Praxair-Trailgaz Unizone tMlo corona discharge ozone generator) from compressed air or source of oxygen, produce.Then this ozone that comprises air-flow 36 be leading to a pump 38 (for example, Teledyne ISCO 500D syringe pump), and wherein, this wraps air-flow ozoniferous and fills this raw material storage tank 40.These storage tank 40 inclusions are compressed to a pressure that is suitable for being incorporated into reaction member 12.Superfluous ozone by pipe 42 that exhaust stream is filled through a magnesia catalyst then bubbling by a kind of sodium hydrate aqueous solution 44 and destroyed.The input port 18 of bottom left end is used for introducing carbon dioxide and/or introducing nitrogen from a nitrogenous source 48 from a carbon dioxide source 46 entering reaction member 12, and removes product ending reaction time.Product is by being collected this product stream bubbling by a chilled solvent 50.Top opening 28 has a rupture pressure disc 30 and also can be used for product-collecting.
2. in order to guide at CO 2test in expanded solvents, following mixture is at dense CO 2in compatibility and volumetric expansion can be in the running temperature (10-25 ℃ or 282.15-298.15K) of standard at one in observation unit, determine.Should the explanation of observation unit and this test method expanding for measurement volumes be (Ghezai Musie elsewhere, Ming Wei, BalaSubramaniam, and Daryle H.Busch, " Catalytic Oxidations in Carbon Dioxide-basedReaction Media, including novel CO 2-expanded phases, " Coord.Chem.Revs., 219-221,789-820 (2001); Ming Wei, Ghezai T.Musie, Daryle H.Busch and BalaSubramaniam, " CO 2-expanded Solvents:Unique and Versatile Media for PerformingHomogeneous Catalytic Oxidations, " J.Am.Chem.Soc., 124,2513-17 (2002)) provide.
3. test is implemented to determine liquid phase O 3concentration.At one at liquid CO 2in determine in the type testing of ozone concentration, a large amount of CO 2by a mouth, be introduced into this unit (temperature maintains the temperature of a requirement) until reach CO 2form the pressure of liquid phase and record the pressure of unit.Liquid level in this unit reaches higher than window and makes ultraviolet ray/visible spectrum path when this liquid phase complete.Gas (O from this ozone generator output 2/ O 3mixture) use ISCO syringe pump to be compressed to one higher than the pressure of this unit pressure.Wrapping mixture ozoniferous is then allowed through an entrance and enters this unit and being allowed at liquid phase CO 2ultraviolet ray/visible spectrum measured with forward horizontal stand.More ozone is repeatedly added, and carries out once ultraviolet ray/visible spectrum and measure after adding each time, follows balance, until the expection pressure that reaches capacity.
Ozone has two and absorbs light section, a λ in ultraviolet ray/visible range maxstrong section of=253.7nm and two maximum are at 577nm and 603nm weak section (respectively referring to accompanying drawing 4A and 4B).At these wavelength, by the light intensity of Ozone Absorption, be directly proportional to the concentration of ozone, therefore, absorption value can be used to measure ozone concentration.Selecting the Chappuis section of visible region, is in the absorption value that is applicable to studied ozone concentration because of its light intensity.
Absorbance at 580nm place is measured for the ozone solution in liquid carbon dioxide (T=5.0 ± 0.2 ℃ or 277.15 ± 0.2K, P=63.4 ± 1.4bar).Then this solution of a known volume (0.52mL) be sampled in a stainless steel tube (accompanying drawing 3).This sampling is allowed to expand at leisure room temperature and constant pressure (R.T.P), and escaping gas is passed through a potassium iodide aqueous solution by bubbling.Then this pipe uses compressed air rinsing, and it is also passed through a KI solution by bubbling.This KI solution is with 4 * 10 -4mol dm -3na 2s 2o 3titration is to determine iodine concentration.Pressure slight decline in unit is by pumping into more O 3/ O 2admixture of gas is compensated, and this process is repeated three times.The value of ε is presented in table 1.
Table 1
Operation O in 0.52ml sample 3Concentration (mol dm -3) At the Abs. of 580nm place ε (dm 3mol -1cm -1)
1 2.11×10 -3 0.159 29.6
2 1.69×10 -3 0.137 25.4
3 3.02×10 -3 0.201 26.2
4 2.98×10 -3 0.184 24.3
4. when the gas output of this ozone generator is compressed into reaction member with syringe pump, ozone concentration is with linear the increasing of overall pressure (supposition is perfect gas under this ISCO pump condition).Because the molar fraction of ozone in this output stream is constant, should correspondingly with overall pressure, increase.Above-mentioned feature is proved in Fig. 5 and Fig. 6, wherein O 2with air as ozone production source gas.
5. when when-0.7 ℃ (or 272.45K) measurement is dissolved in the ozone concentration of liquid carbon dioxide, do not observe this linear behavio(u)r (accompanying drawing 7 and 8).A large amount of liquid carbon dioxides are introduced into this unit, cause gas in unit/liquid contact-making surface sufficiently high, and spectrophotometric light path runs through this test all in this liquid phase.From the gas of this ozone generator output, then with this syringe pump, compressed, this ozone mixture is passed a titanium glass raw material and pumps into the mixing of liquid carbon dioxide to have guaranteed.At one section, for reaching after the time of balance, the ozone concentration in this liquid carbon dioxide is then by spectrophotometer measurement.Owing to approaching the critical pressure (808psi, 55.7bar) of ozone, the quantity that is dissolved in the ozone of this liquid carbon dioxide significantly increases.At 53.1bar, the ozone concentration in liquid phase is approximately 0.005 unit.Yet, at 62.1bar, ozone Nong Suwei 0.05 unit in liquid phase, the violent raising of exceedance magnitude.Similarly situation can be observed in certain range of temperature.
The use of 6.CXLs has lot of advantages with respect to the use of traditional neat solvent.By replace a pith of conventional organic solvents with carbon dioxide, this CXL mixture has improved mass transfer and reaction rate, has reduced waste, and makes reactor nature safer.A variety of substrates have than solubility higher in pure liquid state or supercritical carbon dioxide in CXLs in addition.CXL is by the carbon dioxide expanded conventional solvent with supercharging to produce a single-phase mixture, and wherein, a measurable part of this liquid volume is attributable to this compression arbon dioxide.Photographic data (not shown) shows, the expansion of methyl alcohol has formed a kind of CXL.Meniscus shows that whole volume is in the increase of this condition (carbon dioxide of 52.7bar) lower nearly 120%.
7. methyl alcohol/soya-bean oil binary composition is at CO 2the temperature effect of upper expansion is studied.Under 296.15K, 323.15K and 338.15K condition, with the methyl alcohol soya-bean oil binary composition of carbon dioxide expanded a kind of 6: 1.As shown in Figure 9, in the temperature of 296K, when pressure increases, V/Vo has a more great change.CO 2provide with the compatibility of this methyl alcohol/soya-bean oil binary composition the chance that improves ozone dissolved degree and the oxidation of safe selectivity organism resource for finding in this CXL system, as mentioned above.
8. utilizing the advantage of this CXLs is attractive target for ozonolysis reactions.Yet, studies have shown that, the selection of carbon dioxide expanded solvent is important, because the reactivity of ozone causes it to be promptly oxidized a lot of organic solvents under boosting forming CXL.When ozone is added to CO 2expansion methyl alcohol does not observe the aobvious light section (accompanying drawing 10) that has ozone feature on ultraviolet ray/visible spectrum.When being added to n-hexane CXL (accompanying drawing 11), ozone can obtain same observation.Report has widely, yet ozonolysis reactions can carry out in organic solvent, specifically methyl alcohol.We measure ozone concentration in clean methyl alcohol attempt at 1.013bar and-4 ℃ (268.15K) does not have the concentration (accompanying drawing 12 of the ozone of measurable dissolving in being presented at this solvent; T=276.15K, P=1.013bar, 1500mL ozone solution 50%, 1.0A; O 2source@200cfm, ozone bubbling passes through solvent).In addition, substrate methyl oleate joins ozone by the methyl alcohol sample of its bubbling, has shown responseless evidence (accompanying drawing 13).Yet, the ultraviolet ray/visible spectrum (accompanying drawing 14 after this ozone joins the methanol solution of methyl oleate; T=276.15K, P=1.013bar, 0.5mL methyl oleate is in 9mL methyl alcohol) in ultraviolet range with a strong absorber portion (λ max=284nm) shown the formation of product.These observations show, the easy Oxidation of Methanol of ozone, but, in dynamics, with the reaction of methyl oleate, be preferred.This can provide an indication, and substrate is that solvent can be the target (for example, methyl oleate is as substrate and solvent) of ozone oxidation.
9. ozone decomposed test is implemented in different substrates.In a typical substrate ozone decomposed test, substrate is introduced into the reaction member that maintains environmental stress and predetermined reaction temperature, next, and CO 2be added into produce a liquid phase.Utilize ISCO pump, wrap gas ozoniferous and be then pumped to this reaction member to reach one higher than CO 2the predetermined pressure of/substrate mixture pressure.Next, during reaction, ozone concentration spectrophotometer measurement.In the ending of this intermittent reaction, sample by a cold-trap that effluent is reduced pressure (maintaining-78 ℃ or 195.15K) from this CO 2in liquid phase, take out, in this cold-trap, sample is collected, and analyzes subsequently with GC/MS.
10. work as O 2and O 3when the pressure of admixture of gas increases, by ultraviolet ray/visible light light-splitting photometry, measure the concentration of ozone soluble in water.The luminous intensity absorbing for ozone at 580nm place is directly proportional to the concentration of ozone, and therefore, absorption value can be used as the measurement of ozone concentration.In typical a measurement, water be introduced into this observation unit so that gas-liquid contact face just in time higher than the fibre-optic spectrophotometric light path of this marine optics.This unit is then sealed, and temperature allows to reach balance.Temperature is controlled by the aluminium chuck with this observation unit thermo-contact with a cold bath circulation heat transfer fluid.The output gas of ozone generator is then by with ISCO syringe pump compression with pump into this observation unit.When pressure increases, carry out spectrophotometry.After pressure increases each time, before carrying out a spectrophotometry, unit inclusion is thoroughly stirred at least two minutes with a magnetic stirrer rod.
Spectrum record at a series of pressure and temperature (accompanying drawing 15,16, and 17) declare publicly, the concentration of ozone soluble in water is as linear the increasing of function of pressure.When existing in liquid carbon dioxide, when ozone critical pressure (808psi, 55.7bar) is crossed in pressure increase, the ozone concentration in water does not have enhancing sharply.
11. in a typical test, is placed in reaction under high pressure unit at the bottom of the alkylene of known quantity, and carbon dioxide is added to the pressure of 44.8bar.This solution is cooled to reaction temperature, and then, the admixture of gas of ozone and oxygen is added this reaction member with an ISCO syringe pump, until add at least one dual ozone exceeding the quata.Mixture reaction some hours, with stirring.The liquid CO of the mixture of product-collecting by leisure this being comprised to methyl alcohol, n-hexane or carrene 2part is ventilated and is undertaken by a cold-trap (0 ℃ or 273.15K).CO is used in this unit then 2supercharging again, and pass through for the second time cold-trap.Solvent wash is collected twice with this in this unit then.By GC/MS, adopt relevant internal standard to carry out product analysis.Major product for the substrate of each research is presented in table 2.
Table 2
Substrate Mix Conversion ratio Product
Methyl oleate (is insoluble to liquid CO 2) Machinery 24％ Aldehyde C-9 azelaic acid, monomethyl ester n-nonanoic acid
Methyl oleate Ultrasonic wave 100％ Aldehyde C-9 9-oxo-methyl pelargonate azelaic acid, monomethyl ester n-nonanoic acid
Fan Shi talan (dissolves in liquid CO 2) Machinery 95％ Benzaldehyde phenylamino benzoic acid Ethyl formate phenol methyl-n-butyl ketone
Shun Shi talan (dissolves in liquid CO 2) Machinery 85％ Benzaldehyde benzoic acid phenol
Cyclohexene Machinery 99％ Polymer caproic acid 1,1 ' oxygen two (n-hexane)
Propylene Machinery Polymer acetic acid cyclopentyl alcohol
Forulic acid Ultrasonic wave ＞80％ Vanillin phenol
As shown in figure 18, a reaction under high pressure system 60 of structure.This reaction under high pressure system 60 comprises the feature shown in many accompanying drawings 3.This reaction under high pressure system 60 also comprises a high pressure titanium reaction member 62 (accompanying drawing 18) of including ultrasonic probe 64 in.Ultrasonic probe 64 extends into this reaction member 62 and is connected with a fixed head 66.This fixed head is further connected with a ultrasonic transducer 68, and this ultrasonic transducer 68 is from signal generator 70 reception high frequency inputs and for this ultrasonic probe 64.
Reaction system 60 is used at liquid CO 2the emulsion of the insoluble substrate of middle generation, to strengthen substrate and O 2between reaction interphase mass transfer.When bag solution ozoniferous is subject to ultrasonic wave mixing, the stability of ozone is also studied.
In water, ultrasonic wave stirs and demonstrates the speed that increases ozone decomposed with at least two orders of magnitude, as accompanying drawing 19 (Kang, J-W., Lee, K-H., Koh, C-I., Nam, S-N., Korean Journal of Chemical Engineering 18336 (2001)) shown in.Our research shows, uses concentrated phase carbon dioxide there is no this effect (accompanying drawing 20), and the chances are because the absence of ozone typical free radicals propagation steps of decomposition mechanism in water.
The present invention can show with other the concrete form that does not depart from its spirit or substantive characteristics.The described specific embodiment is in all fields only as illustrative and nonrestrictive consideration.Therefore, scope of the present invention is by additional claim but not represents by above-mentioned explanation.All variations in claim method and scope full scope of equivalents are all included within the scope of it.All parts of all including in herein of specifically quoting herein.
Content disclosed by the invention is not subject to the restriction of the specific specific embodiment described in this application, and it is intended to the explanation as different aspect.Can have the modifications and variations that much do not depart from its spirit and scope, this will be apparent to those skilled in the art.The method and apparatus of function equivalent is within the scope of the present invention enumerated except those herein, is apparent to those skilled in the art from above stated specification.This modifications and variations also drop in the scope of accessory claim.The present invention is only limited by the term of accessory claim, and gamut equals the restriction of the theme of claim.Be understandable that, the present invention is not limited to specific method, reagent, compound component or biological systems, and certainly, they can be different.Also be understandable that, term used herein is for describing the object of the specific specific embodiment, but not for restriction.
For the application of any plural number and/or singular references herein, those skilled in the art can translate into odd number and/or translate into plural number to be adapted to context and/or application from odd number from plural number.The displacement of different singular/plural can be illustrated significantly because of cause clearly.
It will be appreciated by those skilled in the art that, conventionally, particularly accessory claim is (for example herein, additional claim group) term using in as " open " term (is for example generally, term " comprises (including) " and should be interpreted as including but not limited to, term " has (having) " should be interpreted as having at least one, and term " comprises (includes) " and should be interpreted as including but not limited to, etc.).Those skilled in the art are further understandable, if a concrete number is described when the narration of quoting claim, such purpose will be enunciated in this claim, there is no this narration, just there is no such purpose.For example, in order to contribute to understand, following additional claim can comprise guiding phrase " at least one " and " one or more " to guide the description of claim, yet, the use of this phrase should not be regarded as narration for inferring this claim and by indefinite article " (a) " or " one (an) ", limit any specific rights that comprises this guiding phrase and require to comprise the specific embodiment of only having a this narration, even if identical claim all comprises phrase " one or more " or " at least one " of this guided bone, with indefinite article as " one (a) " or " one (an) " (for example, " one (a) " or " one (an) " should be interpreted as referring to " at least one " or " one or more "), this is also applicable to use the narration of specifying article guiding claim.In addition, even if one for guiding the concrete number of claim narration by clear and definite narration, those skilled in the art also should admit that number that this narration should be interpreted as being used in reference at least this narration (for example, simple narration " two " and without other modifier, the meaning refers at least two, or two or more).In addition, in the following cases, wherein, use an agreement that is similar to " at least one of A, B and C " etc., conventionally, such a structure indication in a sense can be understood by those skilled in the art (for example, having at least one the system of A, B and C by including, but not limited to having system of A, B, C, A and B, A and C, B and C or A and B and C etc.).In addition, in the following cases, wherein, use an agreement that is similar to " at least one of A, B and C " etc., conventionally, such a structure indication in a sense can be understood by those skilled in the art (for example, having at least one the system of A, B and C by including, but not limited to having system of A, B, C, A and B, A and C, B and C or A and B and C etc.).Those skilled in the art are further understandable, in fact the word of any separation and/or phrase represent two or more alternative terms, no matter be in description, claim or accompanying drawing, should be understood to expect the possibility that comprises this term, any one this term or two terms.For example, phrase " A or B " should be understood to the possibility that comprises " A " or " B " or " A and B ".
In addition, the feature in description or aspect are described with the form of Markush group, one of skill in the art will recognize that this description also can the independent element of any this Markush group or submolecule group's formal description.
It will be appreciated by those skilled in the art that, for any and all objects, as provide a written description aspect, all scopes disclosed herein also comprise any and all possible subrange and combination thereof.Any scope of listing can easily be admitted for describing fully, and dividing equally of identical scope being divided at least equate, trisection, the quartering, five deciles, ten deciles etc.As a unrestriced embodiment, each scope of herein inquiring into can be easily decomposed into a bottom trisection, middle trisection and top trisection etc.Those skilled in the art are also understandable, and all wording comprises the number of this narration as " reaching ", " at least ", " being greater than ", " being less than " etc., and refer to and can be decomposed into subsequently the scope of subrange as mentioned above.Finally, those skilled in the art are also understandable, and a scope comprises each independently composition.Therefore, for example, a group with 1-3 unit refers to the group with 1,2 or 3 unit.Similarly, a group with 1-5 unit refers to the group with 1,2,3,4 or 5 unit, etc.
Different aspects and the specific embodiment are open herein, and other aspect and the specific embodiment are also apparent to those skilled in the art.Different aspect disclosed herein and the specific embodiment are used for the object illustrating but not mean restriction, and real scope and spirit represent by following claim.

Claims (12)

1. on the molecule in liquid, carry out a method for ozone decomposed, the method comprises:
A kind of composition that contains liquid and ozone is provided, wherein said liquid is liquid carbon dioxide or carbon dioxide expanded solvent, described ozone carrys out the bag air-flow ozoniferous that uses air or oxygen to make in comfortable ozone generator, this liquid and combined with ozone thing have the temperature of 1 to 1.2 times of ozone critical-temperature and the pressure of 0.5 to 2 times of ozone critical pressure increases ozone concentration in liquid, described temperature uses K as unit, wherein, this molecular melting or be dispersed in this liquid;
Make this molecule and ozone reaction.
2. method as claimed in claim 1, further comprises:
Ozone is introduced to this liquid, and wherein, this liquid and combined with ozone thing have the temperature of 1 to 1.2 times of ozone critical-temperature;
The pressure to 0.5 that isothermal increases the ozone in this liquid to 2 times of ozone critical pressures to increase the ozone concentration in this liquid.
3. method as claimed in claim 2, further comprise this molecule is introduced one of following:
Do not introduce the liquid of ozone;
Do not import the ozone in liquid;
Or introduce the composition of this liquid and ozone.
4. method as claimed in claim 3, wherein, the group that this molecule selects free unrighted acid, fatty acid ester, fatty acid amide and benzyl to form.
5. method as claimed in claim 1, further comprises and provides ultrasonic wave to stir to this liquid and ozone.
6. method as claimed in claim 1, wherein, described liquid is liquid carbon dioxide, wherein this liquid and combined with ozone thing have λ maxat the absorption spectral coverage of 253.7nm, 577nm and 603nm, wherein, when pressure is during lower than 0.5 times of ozone critical pressure, at least one this λ maxthe ODU with Yi Ge 0.005 unit; When pressure is 0.5 to 2 times of ozone critical pressure, this λ maxthere is the ODU of 0.01 to 0.1.
7. method as claimed in claim 1, wherein, described liquid is carbon dioxide expanded solvent, wherein this liquid and combined with ozone thing have λ maxat the absorption spectral coverage of 253.7nm, 577nm and 603nm, wherein, when pressure is during lower than 0.5 times of ozone critical pressure, at least one this λ maxthe ODU with Yi Ge 0.005 unit; When pressure is 0.5 when about 2 times of ozone critical pressures, this λ maxthere is the ODU of 0.01 to 0.1.
8. method as claimed in claim 2, wherein, the step of the pressure of the ozone in this liquid of described increase comprises and is increased to 0.75 to 1.5 times of ozone critical pressure to increase the step of the ozone concentration in this liquid, described liquid is liquid carbon dioxide.
9. method as claimed in claim 2, wherein, the step of the pressure of the ozone in this liquid of described increase comprises and is increased to 0.9 to 1.35 times of ozone critical pressure to increase the step of the ozone concentration in this liquid, described liquid is liquid carbon dioxide.
10. method as claimed in claim 2, wherein, the step of the pressure of the ozone in this liquid of described increase comprises and is increased to 0.95 to 1.25 times of ozone critical pressure to increase the step of the ozone concentration in this liquid, described liquid is liquid carbon dioxide.
11. methods as claimed in claim 1, wherein, described molecule is aliphatic acid or their ester.
12. methods as claimed in claim 1, wherein, described molecule is for having allylic molecule.
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